Endothermic Charge Separation Occurs Spontaneously in Non‐Fullerene Acceptor/Polymer Bulk Heterojunction

Organic photovoltaics (OPVs) based on non‐fullerene acceptors (NFAs) have achieved a power conversion efficiency close to 20%. These NFA OPVs can generate free carriers efficiently despite a very small energy level offset at the donor/acceptor interface. Why these NFAs can enable efficient charge separation (CS) with low energy losses remains an open question. Here, the CS process in the PM6:Y6 bulk heterojunction is probed by time‐resolved two‐photon photoemission spectroscopy. It is found that the CS, the conversion from bound charge transfer (CT) excitons to free carriers, is an endothermic process with an enthalpy barrier of 0.15 eV. The CS can occur spontaneously despite being an endothermic process, which implies that it is driven by entropy. It is further argued that the morphology of the PM6:Y6 film and the anisotropic electron delocalization restrict the electron and hole wavefunctions within the CT exciton such that they can primarily contact each other through point‐like junctions. This configuration can maximize the entropic driving force. Endothermic charge separation is found to occur spontaneously in a non‐fullerene acceptor (NFA)‐based bulk heterostructure (PM6:Y6), which can be driven by entropy. This process can produce free carriers even with a small interfacial energy level offset, which can contribute to the high performance found in recent NFA organic photovoltaics.